Complexed p-phenylenediamine containing photographic element and development process therefor

ABSTRACT

COLOR PHOTOGRAPHIC ELEMENTS COMPRISING A SUPPORT COATED WITH AT LEAST ONE HYDROPHILIC COLLOID LAYER CONTAINING LIGHT-SENSITIVE SILVER HALIDE AND A NONDIFFUSIBLE COUPLER THAT REACTS WITH OXIDIZED AROMATIC PRIMARY AMINE COLOR DEVELOPING AGENT TO FORM A NONDIFFUSIBLE DYE AND COATED ON THE SAME SIDE OF THE SUPPORT AT LEAST ONE HYDROPHILIC COLLOID LAYER CONTAINING A PHOTOGRAPHICALLY COMPATIBLE, INACTIVE COLOR DEVELOPING AGENT PRECURSOR FORMED BY REACTING (1) A WATER-SOLUBLE POLYVALENT METAL SALT WITH (2) A WATER-SOLUBLE AND DIFFUSIBLE P-PHENYLENEDIAMINE COLOR DEVELOPING AGENT OR ACID SALT THEREOF. THE IMMEDIATE ELEMENTS HAVE GOOD STABILITY WITH SUBSTANTIALLY NO CHANGE PRODUCED BY TTHE COLOR DEVELOPING AGENT PRECURSOR DURING STORAGE AND ARE ADVANTAGEOUSLY COLOR DEVELOPED BY CONTACTING THE PHOTOGRAPHIC ELEMENT WITH AN AQUEOUS ALKALINE ACTIVATOR SOLUTION WHICH RAPIDLY RELEASES ACTIVE COLOR DEVELOPING AGENT FROM THE PRECURSOR.

United States Patent Int. Cl. G03c 7/00 U.S. Cl. 96-55 24 ClaimsABSTRACT OF THE DISCLOSURE Color photographic elements comprising asupport coated with at least one hydrophilic colloid layer containinglight-sensitive silver halide and a nondiffusible coupler that reactswith oxidized aromatic primary amine color developing agent to form anondiffusible dye and coated on the same side of the support at leastone hydrophilic colloid layer containinga photographically compatible,inactive color developing agent precursor formed by reacting (1) aWater-soluble polyvalent metal salt with (2) a Water-soluble andditfusible p-phenylenediamine color developing agent or acid saltthereof. The immediate elements have good stability with substantiallyno change produced by the color developing agent precursor duringstorage and are advantageously color developed by contacting thephotographic element with an aqueous alkaline activator solution whichrapidly releases active color developing agent from the precursor.

This invention relates to light-sensitive photographic silver halideelements, more particularly to photographic silver halide elements whichcontain a photographically compatible precursor of a color developingagent.

In the preparation of silver halide emulsions for recording colors, itis customary to incorporate a color-forming material in the silverhalide emulsion so that upon color development, this color-formingcompound (coupler) reacts with the oxidation product of the developingagent to form a dye. In the typical emulsion for recording within thevisible spectrum, the emulsion is coated in several layers, eachsensitive to a particular region of the spectrum. By suitable control ofthe development and by use of appropriate couplers,,it is possible toform the proper dye in each layer to give an adequate colorrepresentation of the light image-producing the original exposure.Subsequently, the silver image formed during the color development stepand residual silver halide in the photographic element are removed bybleaching and then fixing or, alternatively, by a combined bleach-fixbath leaving the dye image reproduction in the photographic element.

A p-phenylenediamine color developing agent is most commonly used forthe color development of color photographic elements. Thep-phenylenediamines are used in color developing baths since it has notbeen feasible to incorporate these developers in a silver halideemulsion or in another hydrophilic colloid layer of the photographicelement adjacent to the silver halide emulsion layer. The incorporationof color developing agents in photographic emulsions generally givesrise to basic problems such as desensitization, increased fog and/orspeed loss during storage of photographic material. Accordingly, it hasbeen desirable to find a means of incorporating a p-phenylenediaminedeveloper or precursor thereof in the photographic element and, at thesame time, to provide a stable photographic element which can be storedwithout change in photographic quality.

Barr U.S. Pat. 3,295,978 describes the incorporation of metal salts ofblack-and-white developers, such as catechol and hydroquinone inphotographic silver halide emulsion ice layers. After image exposure,these photographic elements are developed by treating the element withan activator solution containing an anion, such as sulfate, sulfite,thiocyanate, chloride, bromide, iodide, etc., which is capable offorming a less dissociated compound than the precursor with the metalions from the precursor at a pH high enough to activate the developingagent freed from the precursor, usually pHs of about 11 cause imagedevelopment. The exact structure of the metal salts of these developersused as developing agent precursors is not known with certainty.

Harnish et al., U.S. Pat. 3,342,597 describes the use of indoanilinedyes as developing agent precursors in photographic elements.

Other photographic elements are desired which contain other precursorsof color developing agents, preferably precursors which have little, ifany, color, which do not cause any stability problems on storage andwhich are rapidly activated by an activator solution during thedevelopment step.

It is, therefore, an object of our invention to provide a novel colorphotographic element containing a photographically compatible precursorof a p-phenylenediamine color developing agent which has good stabilityduring storage and does not show desensitization, increased fog and/ orspeed loss during storage.

Another object of our invention is to provide a novel photographic colorelement containing photographically compatible color-developing agentprecursors which not only have good stability on storage, but whichrelease the active color developer at a rapid rate when treated with anactivator bath during photographic processing.

Another object of our invention is to provide a novel process forforming a dye image in a photographic silver halide element containing aprecursor of a color developing agent by simply contacting theimage-exposed element with an aqueous alkaline activator solution.

Still further objects of our invention will become evident from theconsideration of the following specification and claims.

These and still other objects of our invention are accomplishedaccording to our invention by preparing and using our color photographicelement comprising a support having coated thereon at least onehydrophilic colloid layer containing silver halide and on the same sideof the support at least one hydrophilic colloid layer containing atleast one of our photographically compatible color developing agentprecursors that is the reaction product of (1) a water-soluble salt of apolyvalent metal and (2) a water-soluble and diifusiblep-phenylenediamine color developing agent. Our novel photographicelements have good stability upon storage, but rapidly release activep-phenylenediamine color developing agent when treated with aqueousalkaline solution. By a photographically compatible developing agentprecursor, we mean any such precursor which, when incorporated into orcontiguous to a lightsensitive silver halide emulsion, does notadversely affect the sensitometric properties of the silver halideemulsion such as speed, fog, contrast and the like.

The water-soluble salts of polyvalent metals, preferably divalentmetals, used in preparing the developer precursors used in thisinvention, include those represented by the formula:

wherein M+ represents a polyvalent metal, such as, cadmium, copper,lead, zinc, etc.; q represents an integer of 2 or 3, the valence of themetal; r represents an integer of 1 or 2; X represents an acid anion,such as, chloride,

The water-soluble and ditfusible p-phenylenediamine color developingagents used to advantage in the developer precursors used in theinvention include those having the formula:

cupric nitrate cupric sulfate lead chloride lead chlorate lead acetatezinc chloride zinc bromide zinc iodide zinc chlorate zinc nitrate zincsulfate zinc acetate IFIHa a R (HEX- T wherein R, R R and R are the sameor diiferent and include hydrogen, an alkyl group of from 1 to 5 carbonatoms, such as, alkyl (e.g., methyl, ethyl, propyl, butyl, amyl, etc.),substituted alkyl, such as, hydroxy alkyl (e.g., hydroxymethyl,hydroxybutyl, etc.), a haloalkyl group (e.g., chlorocthyl, bromoethyl,etc.), a sulfoalkyl group (e.g., sulfoethyl, sulfopropyl, sulfobutyl,etc.), a carboxyalkyl group (e.g., carboxymethyl, carboxyethyl,carboxybutyl, etc.), an alkylsulfonamido alkyl group (e.g.,methylsulfonamidomethyl, ethylsulfonamidomethyl, etc.), an alkoxy grouphaving from 1 to 5 carbon atoms (c.g., methoxy, ethoxy, propoxy,amyloxy, etc.); or acetamido; X- represents an anion, such as, chloride,bromide, iodide, acetate, nitrate, chlorate, bromate, sulfate, etc.; mrepresents an integer of from '1 to '2, the valence of X; and nrepresents an integer of from 1 to 3.

Photographically compatible inactive color developing agent precursorsuseful in the invention include those represented by the formula:

(III) NH:

Dichloro-p-pheny1enediamine cadmium II or as the dimertetrachloro-a-dl-(p-phenylenediamine)di-cadmium (II)Dich10ro-p-phenylenediamine zinc (II) or as the dimertetrachloro-c-di-(p-phenylenediamine)dizrnc (II)Dichloro-p-phenylenediamine copper (II) or as the dimertetrachloro-a-dip-phenylenediamine dicopper (II)Dichloro-p-phenylenediamine lead (II) or as the dimertetrachloro-a-di-(p-phenylenediamine)dilead (II)Dinitrate-p-phenylenediamine cadmium (II) or as the dimertetranitrate-n-dip-phenylenediamine) dicadmium (II)Sulfatodiaquo-p-phenylenediamine cadmium (II) or as the dimerId)isulfatotetraaquo-nflb p-phenylenediamine) dicadmiumDiacetoxy-p-phenylenediamine cadmium (II) or as the dimertetraacetoxy-a-di- (p-phenylenediamine) dicadmium (II)Dibromato-p-phenylenediamine cadmium (II) or as the dimertetrabromato-u-di- (p-phenylenediamine) dicadmium (II)Dibromop-phenylenediamine cadmium (II) or as the dimer tetrabrom0u-di-(p-phenylenediamine) dicadmium (II) [P* 6 4 a z] CdCLf D-nylenediaminium tetrachlorocadmiumate (II) ITIH:

CHa

[CdCsl'HzO 1- (N,N-diethy1) -3-methyi-4-pheny1enediaminiumtrichloroaquocadmiumate (II) 1' (N-ethyl-N-fl-hydroxyethyl -3-methyl-4plienylenediaminium dichlorosulfatocadmiumate (II) 1- (N,N-diethyl-3-H-methanesulfonamidoethyl-4-phenylenediaminium tetrachlorocadmiumate(II) These and other color developing agent precursors formed by thereaction of (1) a water-soluble polyvalent metal salt with (2) awater-soluble and dilfusible aromatic primary amine color developingagent, preferably a pphenylenediamine color developing agent, are usedto advantage in the invention, including precursors having Formula III.

In general, such developing agent precursors are prepared by mixing anaqueous solution of a water-soluble salt of a polyvalent metal havingthe formula: MX defined previously, into an aqueous solution of awatersoluble and diffusible p-phenylenediamine color developing agent oracid salt thereof and causing the precursor to precipitate. It isadvantageous to use in the range of from equimolar amounts of thereactants to a 400% excess of the salt of the polyvalent metal. It isadvantageous to precipitate the precursors derived from an acid salt ofthe color developing agent by cooling the reaction mixture. Theprecursor is then advantageously purified if desired to remove excessreactants. The purified precursor derived from the acid salt of thecolor developing agent is water-soluble and is advantageously added tothe hydrophilic colloid coating composition in solution. Since ourprecursors derived from the color developing agent per se (i.e., not theacid salt of the developing agent) are not soluble in water, it isadvantageous to precipitate them in the presence of hydrophilic colloidto prevent particles of the precipitating precursor from becoming largerthan is desired. The gelatin solution containing the precipitated develoing agent precursor is advantageously chilled, noodled and washed it itis desired to remove excess reactants.

The preparation of Precursor No. 1 is described in Example 1. Precursors2 through 9 are advantageously prepared in a manner similar to thatdescribed for Precursor No. 1, but using the appropriate reactants. Thepreparation of Precursor No. 10 is described in Example 3. Precursors 11through 14 are prepared in a manner similar to Precursor 10, but byusing the appropriate reactants.

Such precursors of color developing agents are advantageously preparedfrom any of the p-phenylenediamine color developing agents known in theart since they have the pair of electrons needed for complex formation.Some specific types of color developing agents used to advantage aredisclosed in the Journal American Chemical Society, 73, 3100 (1951), R.L. Bent et al.

Our precursors of p-phenylenediamine color developing agents areadvantageously coated in the light-sensitive silver halide hydrophiliccolloid layer(s) and/or in another hydrophilic colloid layer on the sameside of the support (for the photographic element), preferablycontiguous to the light-sensitive layer. It is particularly advantageousto incorporate the developing agent precursors in a layer between thesupport and the light-sensitive layer closest to the support, althoughmany of the precursors have very little, if any, color and areincorporated in the light-sensitive layers. The cupric chloride complexof p-phenylenediamine is black in color and the layer containing itadvantageously serves as a bleachable antihalation layer between thesupport and the first lightsensitive layer as well as a source of activecolor developing agent upon activation during processing.

The color developing agent precursors used in the invention areadvantageously coated in hydrophilic colloid layers of our photographicelements over a wide range of coating rates, preferably so that there isa mole ratio of precursor to silver halide of at least about 1:1.

Our photographic elements are advantageously coated on any of thetypical photographic supports including cellulose nitrate film,cellulose acetate film, polyvinyl acetal film, polystyrene film,poly(ethylene terephthalate) film, polyethylene film, polypropylene filmand related films of resinous materials, as well as paper, glass andothers.

Our photographic elements comprise a support with at least onehydrophilic colloid layer containing silver halide and a nondifiusiblecolor-forming coupler that reacts with oxidized aromatic primary aminecolor developing agent to form a nondiftusible dye and on the same sideof the support at least one hydrophilic colloid layer that contains atleast one of our precursors of a p-phenylenediamine color developingagent. Usually our photographic elements are multicolor and contain twoor more emulsion layers sensitive to difierent regions of the actinicspectrum. In one of our elements, the support is coated in successionwith a layer containing our color developing agent precursor, ared-sensitized silver halide emulsion layer containing a nondiffusiblephenolic or nondiffusible naphthoic cyan-dye forming coupler, agreensensitized silver halide emulsion layer containing a nondiffusiblemagenta-dye-forrning coupler, such as, a 5- pyrazolone coupler, a bluesensitive silver halide emulsion layer containing a nonditfusibleopen-chain yellowdye-forming coupler, either with or without ableachable blue light-absorbing filter layer between the green-sensitiveand blue-sensitive layers, other interlayers, antihalation layer,overcoat layer, etc. The couplers and differently sensitized layers arealso arranged on one or both sides of the support in the same or otherorders.

In photographic elements where there are light-sensitive layers on bothsides of a transparent support, it is advantageous to have a hydrophiliccolloid layer on both sides of the support containing at least one ofour color developing agent precursors. The differently sensitized layersare advantageously double-coated as described in German Pat. 1,121,470,Wolf et al. US. Pat. 3,516,831, etc.

Hydrophilic colloid used to advantage in the silver halide emulsion orfor separate layers containing the feature developing agent precursorinclude gelatin, colloidal albumin, a cellulose derivative or asynthetic resin, for instance, a polyvinyl compound. Some colloids whichmay be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate asdescribed in Lowe US. Pat. 2,286,215, issued June 16, 1942; a farhydrolyzed cellulose ester, such as cellulose acetate hydrolyzed to anacetyl content of 19- 26% as described in Lowe et al. U.S. Pat.2,327,808, issued Aug. 24, 1943; a water-soluble ethanolamine celluloseacetate as described in Yutzy US. 2,322,085, issued June 15, 1943; apolyacrylamide having a combined acrylamide content of 30-60% and aspecific viscosity of 0.25- 1.5 and an imidized polyacrylamide of likeacrylamide content and viscosity as described in Lowe et 'al. US. Pat.2,541,474, issued Feb. 13, 1951; zein as described in Lowe US. Pat.2,563,791, issued Aug. 7, 1951, a vinyl alcohol polymer containingurethane carboxylic acid groups of the type described in Unruh et al.US. Pat. 2,768,154, issued Oct. 23, 1956, or containing cyano-acetylgroups, such as the vinyl alcohol-vinyl cyano-acetate copolymer asdescribed in Unruh et al. US. Pat. 2,808,331, issued Oct. 1, 1957; or apolymeric material which results from polymerizing a protein or asaturated acylated protein with a monomer having a vinyl group asdescribed in Illingsworth et al. US. Pat. 2,852,382, issued Sept. 16,1958. Polyvinyl pyrolidone and mixtures of it with the other hydrophiliccolloids described above are also advantageously used.

Any of the photographic silver halide emulsions, e.g., silver bromide,silver bromoiodide, silver chloride, silver chlorobromide, silverbromochloroiodide, etc., used in photography are used to advantage inour photographic materials. Negative developing-out silver halideemulsions, as well as reversal emulsions such as described in US.2,592,250, can be used.

The emulsions used in the photographic elements of our invention areadvantageously chemically sensitized by any of the accepted procedure.The emulsions can be digestcd with naturally active gelatin, or sulfurcompounds can be added, such as those described in Sheppard US. Pat.1,574,944, issued Mar. 2, 1926; Sheppard et al. US.

7 Pat. 1,623,499, issued Apr. 5, 1927; and Sheppard et al. U.S. Pat.2,410,689, issued Nov. 5, 1946.

The emulsions are advantageously treated with salts of the noble metals,such as ruthenium, rhodium, palladium, iridium and platinum, asdescribed in Smith et a1. U.S. Pat. 2,448,060, issued Aug. 31, 1948 andas described in Trivelli et al. U.S. Pats. 2,566,245 and 2,566,263, bothissued Aug. 28, 1951.

The emulsions are advantageously sensitized with cyanine and merocyaninedyes, such as those described in Brooker U.S. Pats. 1,846,301 and1,846,302, both issued Feb. 23, 1932; and 1,942,854, issued Ian. 9,1934; White U.S. Pat. 1,990,507, issued Feb. 12, 1935; Brooker and WhiteU.S. Pats. 2,122,140, issued Mar. 22, 1938; 2,165,338, issued July 11,1939; 2,493,747, issued Ian. 10, 1950; and 2,739,964, issued Mar. 27,1956; Brooker et al. U.S. Pat. 2,493,748, issued Jan. 10, 1950; SpragueU.S. Pats. 2,503,776, issued Apr. 11, 1950 and 2,519,001, issued Aug.15, 1950; Heseltine et al. U.S. Pat. 2,666,761, issued Jan. 19, 1954;Heseltine U.S. Pat. 2,734,900, issued Feb. 14, 1956; VanLare U.S. Pat.2,739,149, issued Mar. 20, 1956; and Kodak Limited British 450,958,accepted July 15, 1936.

The emulsions also advantageously contain speedincreasing compounds ofthe quaternary ammonium type of Carroll US. Pat. 2,271,623, issued Feb.3, 1942; Carroll et al. U.S. Pat. 2,288,226, issued June 30, 1942; andCarroll et al. U.S. Pat. 2,334,864, issued Nov. 23, 1943; and thepolyethylene glycol type of Carroll et al. U.S. Pat. 2,708,162, issuedMay 10, 1955.

The emulsions are also advantageously chemically sensitized with goldsolts as described in Waller et al. U.S. Pat. 2,399,083, issued Apr. 23,1946, or stabilized with gold salts as described in Damschroder U.S.Pat. 2,597,856, issued May 27, 1952; and Yutzy et a1. U.S. Pat.2,597,915, issued May 27, 1952. Suitable compounds are potassiumchloroaurite, potassium aurithiocyanate, potassium chloroaurate, aurictrichloride and 2-aurosulfobenzothiazole methochloride.

In addition to the addenda already described, our emulsions alsoadvantageously contain any of the wellknown stabilizers; antifoggants;speed-increasing materials, such as polyalkylene oxides, onium salts andthioethers; plasticizers; coating aids, such as anionic, nonionic andamphoteric surface active compounds and the like. In addition to thechemical sensitization of our hydrophilic colloid silver halideemulsions described above, our emulsions are also advantageouslyreduction sensitized with reducing agents.

The various layers of the photographic elements of our invention areadvantageously hardened with any of the known hardeners including, forexample, aldehyde hardeners, aziridine hardeners, hardeners which arederivatives of dioxane, oxypolysaccharides, such as oxystarch, oxyplantgums and the like.

Usually the couplers are used to advantage in our materials and areballasted to make them nondifiusible in the silver halide emulsions inwhich they are incorporated. The couplers utilized in our invention canbe dispersed in a high-boiling, crystalloidal compound which can be usedas a vehicle for incorporating the coupler in the photographic emulsionaccording to methods well known in the art. Various other known methodsof incorporating the color-forming couplers in our element may also beutilized. For example, the low solvent dispersion described in FierkeU.S. Pat. 2,801,107 is used to advantage; or the couplers may bedispersed in natural resin-type solvents as described in Martinez U.S.Pat. 2,284,879; or the couplers may be dissolved in monomeric solutionwhich is then polymerized in the presence of gelatin to producedispersions of the coupler in the polymer as described in U.S. Pat.2,825,382. Alternatively, the color-forming couplers can be of thefat-tail variety, that is, the Fischer type which have solubilizinggroups on them which render them soluble in alkaline solution.

The following examples are included for a further understanding of ourinvention.

EXAMPLE 1 The cadmium chloride complex of p-phenylenediamine is preparedas follows: 10.8 g. of p-phenylenediamine dissolved in 150 ml. of wateris mixed into g. of a 20% bone gelatin solution, then 38.5 g. of cadmiumchloride in ml. of water is added to the mixture with strong stirringand the combined mixture adjusted to 500 g. with water. Into 70 g. of agelatino silver chloride emulsion, having a weight of 7 kg. per gallon,is dispersed 100 g. of a solution of the cyan-forming coupler,l-hydroxy-N- [6-(2,4-di-tert-amylphenoxy)butyl]-2-naphthamide, intricresylphosphate, 50 g. of the cadmium chloride complex ofp-phenylenediamine in gelatin, then 100 ml. of water, 10 cc. of 15%Saponin and 10 ml. of a 2.16% chrome alum solution in water is added andthe resulting coating composition intimately blended. A paper support iscoated with the coating composition at a wet coverage of g./m. to give asilver coverage of about 8 mg. of silver/ dm. This coating is dried, andexposed to a light image to form a latent image in the silver halide.Treatment of the exposed photographic paper for 2 minutes at 20 C. in asolution of 50 g. of sodium carbonate per liter of water gives a cyandye image and a silver image reproduction of the light image used in theexposure. The silver image is removed by treating the developed imagewith a conventional bleach comprising an aqueous solution of potassiumferricyanide, followed by treating the bleached element in aconventional aqueous fixing bath comprising sodium thiosulfate, leavinga cyan dye image reproduction of the light image used in the exposure.

EXAMPLE 2 A piece of the exposed, but unprocessed, photographic papermade in Example 1 is placed in a heat-seal wrapper and incubated for 5days at 50 C. A second piece of the exposed, but unprocessed,photographic paper is held at room temperatures for 5 days as a control.The incubated paper and the control are then processed as described inExample 1 to produce cyan dye image reproductions of the light imageused to make the exposures. The results show the cyan dye imagereproduction in the incubated paper is substantially the same as thecyan dye image in the control.

EXAMPLE 3 The cadmium chloride complex of p-phenylenediamine di-hydrogenchloride is prepared as follows: 18.1 g. of p-phenylenediaminedi-hydrogen chloride is dissolved in 200 ml. of distilled water at 40 C.This solution is treated with a solution of 18.3 g. of cadmium chloridedissolved in 25 ml. of distilled water. The mixture is heated for 5minutes and then cooled to 5 C. to complete the precipitation. The solidcomplex is filtered, washed in ethanol and diethylether, and air dried.The cadmium chloride complex of p-phenylenediamine di-hydrogen chlorideis coated on a cellulose acetate film support from a gelatin solution at3777 mg. of the complex/m2, i.e., in a 1:1 molar ratio to silver. Ared-sensitive sulfur and goldsensitized gelatino silver bromoiodideemulsion containing a dispersion of cyan-dye-forrning naphthol couplerof the type described in Weissberger et al., U.S. Pat. 2,474,293, iscoated over the developer complex layer at 1111 mg. silver and 3022 mg.gelatin per m. One sample of the coating is light exposed overall andanother sample is light exposed to a step tablet test pattern, thenactivated in a 0.1 N sodium hydroxide solution containing a small amountof sodium bromide to decrease background fog, bleached in a conventionalpotassium ferricyanide bleach, fixed in a conventional fixing bathcontaining sodium thiosulfate, washed and dried. The resulting coatingscontain a cyan dye image corresponding to the light exposure given thembefore photographic proc- 9 essing. Density readings made on adensitometer using a red coated filter show a cyan dye D of 1.45 densityunits in the overall exposed sample and a cyan dye D of 0.53 and a D of0.08 density unit in the sample exposed to light through the steptablet.

EXAMPLE 4 Three photographic elements are made by coating on a celluloseacetate film support a gelatin solution containing the addendumindicated in the table below, and over this layer is coated thered-sensitive sulfur and goldsensitized gelatino silver bromoiodideemulsion containing the dispersion of cyan-dye-forming coupler asdescribed in Example 3. A sample of each of the three photographicelements is exposed for /25 second to a step tablet on a sensitometerand processed by pressing them into contact with a gelatin pad which hadbeen imbibed for 60 seconds in an activator bath comprising an aqueoussolution of 1% by weight potassium hydroxide plus by weight of sodiumsulfate. After three minutes, the photographic elements are separatedfrom the gelatin pad, placed in an acid stop bath and then aconventional sodium thiosulfate fixing bath. The D and D values arelisted in the table below.

TABLE Addenda (gJAg mole) cadmium chloride com- Photographic plex ofp-phenyleneresults Element diamine dihydrogen No. chloride Dmin DrunxEXAMPLE 5 Examples 1 and 2 are repeated but using in place of the cyancoupler a nondiffusible magenta-forming 5- pyrazolone coupler of thetype described in Loria et al. US. Pat. 2,600,788. A magenta dye imagereproduction is produced. The magenta dye image in the incubatedphotographic paper is substantially the same as the magenta image in thecontrol.

EXAMPLE 6 Examples 1 and 2 are repeated but using in place of the cyancoupler a nondiffusible yellow-dye-forming coupler of the type describedin McCrossen et al. US. Pat. 2,875,057. A yellow dye image reproductionis produced. The yellow dye image in the incubated photographic paper issubstantially the same as the yellow image in the control.

EXAMPLE 7 Examples 1 and 2 are repeated but instead of using the cadmiumchloride complex of p-phenylenediamine (i.e.,dichloro-p-phenylenediarnine cadmium II), an equivalent amount ofdichloro-p-phenylenediamine zinc (II) is used. This is formed bysubstituting an equimolar amount of zinc chloride for cadmium chloride.Photographic results are obtained that are similar to those obtained inExamples 1 and 2.

EXAMPLE 8 1 and 2.

EXAMPLE 9 Example 8 is repeated but in place ofdichloro-pphenylenediamine cadmium (II), an equwalent amount ofdichloro-p-phenylenediamine copper (II) is used in a 10 layer betweenthe paper support and the light-sensitive layer. Cyan dye images areproduced similar to those obtained in Examples 1 and 2. The coppercomplex in this example is black and the layer containing it serves asan anti-halation coating as well as providing a source of colordeveloping agent when activated with the sodium carbonate solution.

' EXAMPLE 10 Example 8 is repeated using in place ofdichloro-pphenylenediamine cadmium (II), an equivalent amount ofdichloro-p-phenylenediamine lead (II) in the layer between the papersupport and the light-sensitive layer. Cyan dye images are obtained withsubstantially no difference between dye images in the incubated elementand the control element.

EXAMPLE 11 Examples 1 and 2 are repeated using in place ofdichloro-p-phenylenediamine cadmium (II), an equimolar amount ofdichloro-l-(N,N-diethyl)-3-methyl4-phenylenediamine cadmium (II). Cyandye images are obtained similar to those obtained in Examples 1 and 2.

EXAMPLE 12 Example 3 is repeated but using instead of the cadmiumchloride complex of p-phenylenediamine dihydrogen chloride (i.e.,p-chenylenediaminium tetrachlorocadmiumate II), an equivalent amount of1-(N,N- diethyl) 3 methyl 4 phenylenediaminurn trichloroaquocadmiumate(II). A cyan dye image is found similar to that produced in Example 3.Similar results are obtained using equivalent amounts ofl-(N-ethyl-N-phydroxyethyl) 3 methyl 4 phenylenediaminiumdichlorosulfatocadmiumate II or an equivalent amount of 1 (N,N diethyl)3 l3 methanesulfonamidoethyl- 4-phenylenediaminium tetrachlorocadmiumate(II) in place of p-phenylenediaminum tetrachlorocadmiumate (II) inExample 3.

EXAMPLE 13 A paper support is coated on one side in succession with (1)a gelatin layer containing a dispersion of dichloro-p-phenylenediaminecadmium (II) (prepared as described in Example 1), (2) a gelatin layercontaining an ordinary gelatino-silver chlorobromide emulsion that isblue-sensitive and contains a nondiifusible yellow-dyeforming coupler ofthe type described in McCrossen et al. US. Pat. 2,875,057, (3) a gelatinlayer containing an ordinary gelatino-silver chlorobromide emulsion thatis green-sensitized and contains a nondiffusible 5-pyrazolonemagenta-dye-forming coupler of the type described in Loria et al. US.Pat. 2,600,788 and (4) a gelatin layer .containing an ordinarygelatino-silver chlorobromide emulsion that is red-sensitized andcontains a nondifusible cyan-dye-forming coupler of the type describedin Fierke US. Pat. 2,801,171. The dichloro-p-phenylenediamine cadmium(II) is coated so that the mole ratio of this complex to the totalsilver halide is about 3:1. The element is exposed to an original colorimage, then contacted with a solution of 50 g. of sodium carbonate perliter of water until the color image comprising a yellow, magenta, cyandye image along with a silver image is obtained. The developedphotographic element is treated with a conventional acid stop bath,washed, treated with a conventional alkali metal ferricyanide bleachbath, followed by a conventional alkali methal thiosulfate fixing bath,washed and dried. A multicolor dye image reproduction of the originalcolor image is obtained in the processed element.

Similar results are obtained when the light-sensitive layer in thephotographic element of Example 13 are arranged in other orders over thegelatin layer containing one or more of our photographically compatibleand inert color developing agent precursors 1, 2, 3, 4, 5, 6, 7, 8, 9,10, 11, 12, 13 and 14.

EXAMPLE 14 Example 13 is repeated except that the dispersion of ourcolor developing agent precursor dichloro-p-phenylenediamine cadmium(II) in gelatin is dispersed in the light-sensitive layers instead ofbeing coated in a separate layer between the support and theblue-sensitive silver halide emulsion layer. The precursor is coated ineach layer so that the mole ratio of precursor to silver in each layeris about 3:1. A multicolor image reproduction is produced when thiselement is exposed and processed as described in Example 13.

Similar results are obtained when Examples 13 and 14 are repeated usinga conventional film support in place of a paper support.

The alkaline activator solution used for processing our photographicelements is advantageously made alkaline with any of the alkalinecompounds conventionally used in photographic processing solutions,including the alkali metal hydroxides, alkali metal carbonates, borax,etc. Other addenda that are found in color developer solu tions, suchas, silver halide solvents, antifoggants, development accelerators,stabilizers, chemical buifers, etc., are used to advantage in ouractivator solutions. Thickeners used in making viscous processingcompositions are used to advantage in our activator solutions. Ourphotographic element is advantageously developed by contacting it withthe activator solution until the active developing agent is released andthe latent image in the silver halide is developed to silver and dyeimages. The activator solution is applied in viscous form or in liquidform by roller application, by brushing, by immersion, by transfer froma hydrophilic colloid web wet with imbibed solution, etc.

The preparation of color devolping agent precursor Nos. 1, 6 and isdescribed in Chem. Abstracts, 52 page 4335, and the preparation of colordeveloping agent precursor No. 9 is described in Chem. Abstracts, 55,page 2655. These references have no concept of photography or the use ofthe immediate compounds as inactive developing agent precursors. TheChem. Abstracts, 55, page 2655 reference states that the cadmiumchloride complexes of diamines hydrolyzed very slowly (even with boilingdilute sodium hydroxide). It is unexpected from this reference that theimmediate compounds would be activatable and release enough developingagent to develop a silver and dye image when treated at room temperaturefor only 2 or 3 minutes with our alkaline activator solutions.

Our light-sensitive silver halide elements containing ourphotographically inert complexes of polyvalent metal salts withp-phenylenediamine color developing agents as precursors for colordeveloping agents have good stability upon storage; however, ourprecursors in the elements are easily and rapidly activated and silverand dye images developed by treating with alkaline solutions.

The invention has been described in detail with particular reference tocertain preferred embodiments thereof, but it will be understood thatvariations and modifications can be effected within the spirit andscopeof the invention.

We claim: I

1. A photographic element comprising a support having thereon at leastone hydrophilic colloid light-sensitive silver halide layer containingcontiguous to said silver halide a nondiffusible color-forming couplerthat is capable of coupling with oxidized aromatic primary amine colordeveloping agent to form a dye, and on the same side of said support atleast one hydrophilic colloid layer containing a photographicallycompatible inactive color developing agent precursor that is the waterinsoluble, precipitated reaction product of (1) a water-soluble salt ofa polyvalent metal and (2) a water-soluble and dilfusiblep-phenylene-diamine color developing agent.

2. A photographic element comprising a support having thereon at leastone hydrophilic colloid light-sensitive silver halide layer containingcontiguous to said silver halide a nondiffusible color-forming couplerthat is capable of coupling with oxidized aromatic primary amine colordeveloping agent to form a dye, and on the same side of said support atleast one hydrophilic colloid layer containing a photographicallycompatible inactive color developing agent precursor that is the waterinsoluble, precipitated reaction product of (1) a water-soluble salt ofa polyvalent metal and (2) a water-soluble and diffusiblep-phenylenediamine color developing agent having the formula:

IIIH:

ll Rr R wherein R, R R and R each represent a member selected from theclass consisting of hydrogen, an alkyl group having from 1 to 5 carbonatoms, an alkoxy group having from 1 to 5 carbon atoms and an acetamidogroup.

3. A photographic element comprising a support having thereon at leastone hydrophilic colloid light-sensitive silver halide layer containingcontiguous to said silver halide a nondiifusible color-forming couplerthat is capable of coupling with oxidized aromatic primary amine colordeveloping agent to form a dye, and on the same side of said support atleast one hydrophilic colloid layer containing a photographicallycompatible inactive color developing agent precursor that is the waterinsoluble, precipitated reaction product of (1) a water-solublepolyvalent metal salt and (2) a water soluble and diifusiblepphenylenediarnine color developing agent having the formula:

N R2 R1 wherein R, R R and R each represent a member selected from theclass consisting of hydrogen, an alkyl group having from 1 to 5 carbonatoms, an alkoxy group having from 1 to 5 carbon atoms and an acetamidogroup; X represents an anion; m represents the valence of said anion, aninteger of 1 or 2; and n represents an integer of from 1 to 3.

4. A photographic element comprising a support having thereon at leastone hydrophilic colloid light-sensitive silver halide layer containingcontiguous to said silver halide a nondirlusible color-forming couplerthat is capable of coupling with oxidized aromatic primary amine colordeveloping agent to form a dye, and on the same side of said support atleast one hydrophilic colloid layer containing a water insoluble,precipitated photographically compatible inactive color developing agentprecursor selected from those having the formula:

NHz +014) l wherein M represents a polyvalent metal; q represents aninteger of 2 or 3 that is equal to the valence of M; r

represents an integer of 1 or 2; R, R R and R each represent a memberselected from the class consisting of hydrogen, an alkyl group havingfrom 1 to carbon atoms, an alkoxy group having from 1 to 5 carbon atomsand an acetamido group; X represents an anion; m represents an integerof l or 2 that is the valence of X; n is an integer of from 1 to 3; X;represents an anion; p represents an integer of 1 or 2 that is thevalence of X and z represents an integer of from 1 to 5.

5. A photographic element of claim 2 in which said color developingagent precursor is in a hydrophilic colloid layer that is contiguous toand between said hydrophilic colloid layer containing said silver halideand said support.

6. A photographic element of claim 2 in which said color developingagent precursor is in said hydrophilic colloid layer containing saidsilver halide and said colorforming coupler.

7. A photographic element of claim 4 in which q is 2 and r is 1.

8. A photographic element of claim 4 in which q is 2 and r is 2.

9. A photographic element of claim 4 in which in is 1; nis 1 and qis2.

10. A photographic element of claim 4 in which m is l;nis2andqis2.

11. A photographic element of claim 4 in which m is l' nis3andqis2.

12. In a multilayer, multicolor photographic element comprising asupport having thereon a red-sensitive silver halide hydrophilic colloidlayer containing a non-diffusible cyan-dye-forming coupler that reactswith an oxidized aromatic primary amine color developing agent to form acyan dye, a green-sensitive silver halide hydrophilic colloid layercontaining a nondifl usible magenta-dye-forming coupler tha reacts withan oxidized aromatic primary amine color developing agent to form amagenta dye, and a blue-sensitive silver halide hydrophilic colloidlayer containing a nondilfusible yellow-dye-forming coupler that reactswith an oxidized aromatic primary amine color developing agent to form ayellow dye, the improvement comprising the incorporation in at least onehydrophilic colloid layer contiguous to at least one of said silverhalide hydrophilic colloid layers of a water insolube, precipitatedphotographicaly compatible inactive color developing agent precursorhaving the formula:

R3 R (Has) (X- wherein M represents a polyvalent metal; q represents aninteger of 2 or 3 that is equal to the valence of M; r represents aninteger of 1 or 2; R, R R and R each represent a member selected fromthe class consisting of hydrogen, an alkyl group having from 1 to 5carbon atoms, an alkoxy group having from 1 to 5 carbon atoms and anacetamido group; X represents an anion; m represents an integer of 1 or2 that is the valence of X; n is an integer of from 1 to 3; X;represents an anion; p represents an integer of l or 2 that is thevalence of X and z represents an integer of from 1 to 5.

13. A photographic element comprising a support having thereon at leastone hydrophilic colloid light-sensitive silver halide layer containingcontiguous to said silver halide a nondiffusible coupler that is capableof coupling with oxidized aromatic primary amine color developing agentto form a dye, and on the same side of said support at least onehydrophilic colloid layer containing a cadmium chloride complex of ap-phenylenediamine as a color developing agent precursor.

14. A photographic element comprising a support coated with at least onehydrophilic colloid light-sensitive silver halide layer containingcontiguous to said silver halide a nonditfusible coupler that is capableof coupling with oxidized aromatic primary amine color developing agentto form a dye, and on the same side of said support at least onehydrophilic colloid layer containing N Hz CdClz 15. A photographicelement comprising a support having thereon at least one hydrophiliccolloid light-sensitive silver halide layer containing contiguous tosaid silver halide a nondiffusible coupler that is capable of couplingwith oxidized aromatic primary amine color developing agent to form adye, and on the same side of said support at least one hydrophiliccolloid layer containing NHz CdClz ZHCl 16. A photographic elementcomprising a support having thereon at least one hydrophilic colloidlight-sensitive silver halide layer containing contiguous to said silverhalide a nondiflFusible coupler that is capable of coupling withoxidized aromatic primary amine color developing agent to form a dye,and on the same side of said support at least one hydrophilic colloidlayer containing ZnClz 17. A photographic element comprising a supporthaving thereon at least one hydrophilic colloid light-sensitive silverhalide layer containing contiguous to said silver halide a nondifiusiblecoupler that is capable of coupling with oxidized aromatic primary aminecolor developing agent to form a dye, and one the same side of saidsupport at least one hydrophilic colloid layer containing 18. Aphotographic element comprising a support having thereon at least onehydrophilic colloid light-sensitive silver halide layer containingcontiguous to said silver halide a nondiffusible coupler that is capableof coupling with oxidized aromatic primary amine color developing agentto form a dye, and on the same side of said support at least onehydrophilic colloid layer containing CuClz 19. A process for producing aphotographic dye image in an imagewise exposed photographic elementcomprising a support having thereon at least one hydrophilic colloidlight-sensitive silver halide layer containing contiguous to said silverhalide a nonditfusible color-forming coupler that is capable of couplingwith oxidized aromatic primary amine color developing agent to form adye, and on the same side of said support at least one hydrophiliccolloid layer containing a photographically compatible inactive colordeveloping agent precursor that is the water insoluble, precipitatedreaction product of 1) a water-soluble salt of a polyvalent metal and(2) a water-soluble and diffusible p-phenylenediamine color developingagent, said process comprising contacting said element with an aqueousalkaline activator solution which causes said inactive color developingagent precursor to release said water-soluble and diifusiblep-phenylenediamine color developing agent from said precursor, imagewisedeveloping silver halide with the said released color developing agentto silver, and imagewise reacting resulting oxidized color developingagent with said color-forming coupler to produce a photographic dyeimage.

20. A process for producing a photographic dye image in an imagewiseexposed photographic element comprising a support having thereon atleast one hydrophilic colloid light-sensitive silver halide layercontaining contiguous to said silver halide a nondiffusiblecolor-forming coupler that is capable of coupling with oxidized aromaticprimary amine color developing agent to form a dye, and on the same sideof said support at least on hydrophilic colloid layer containing a waterinsoluble, precipitated photographically compatible inactive colordeveloping agent precursor having the formula:

NHz

wherein M represents a polyvalent metal; q represents an integer of 2 or3 that is equal to the valence of M; r represents an integer of 1 or 2;R, R R and R each represent a member selected from the class consistingof hydrogen, an alkyl group having from 1 to 5 carbon atoms, an alkoxygroup having from 1 to 5 carbon atoms and an acetamido group; Xrepresents an anion; m represents an integer of l or 2 that is thevalence of X; n is an integer of from 1 to 3; X represents an anion; prepresents an integer of 1 or 2 that is the valence of X and zrepresents an integer of from 1 to 5, said process comprising contactingsaid element with an aqueous alkaline activator solution having a pH ofat least about 10 which causes aid inactive color developing agentprecursor to release said water soluble and diifusiblep-phenylenediamine color developing agent, imagewise developing silverhalide with the said color developing agent to silver, and imagewisereacting resulting oxidized color developing agent with saidcolor-forming coupler to produce a photographic dye image.

21. A process for producing a photographic dye image corresponding to alatent image in a photographic element comprising a support havingthereon at least one hydrophilic colloid light-sensitive silver halidelayer containing contiguous to said silver halide a nondifrusiblecolor-forming coupler that is capable of coupling with oxidized aromaticprimary amine color developing agent to form a dye, and on the same sideof said support at least one hydrophilic colloid layer containing lTIHz22. A light-sensitive photographic element according to claim 1 in whichsaid one hydrophilic colloid layer containing said photographicallycompatible inactive color developing agent precursor lies adjacent saidone hydrophilic colloid silver halide nondiffusible layer containingsaid nondiifusible color-forming coupler.

23. A photographic element of claim 2 in which said color developingagent precursor is in a hydrophilic colloid layer contiguous to saidsilver halide containing hydrophilic colloid layer.

24. A photographic element of claim 2 in Which said color developingagent precursor is precipitated entirely in a hydrophilic colloid layercontiguous to said silver halide containing hydrophilic colloid layer.

References Cited UNITED STATES PATENTS 2,695,234 11/1954 Jaeken et al.96-66.4 3,295,978 1/1967 Barr 9695 3,342,597 9/1967 Harnish et al. 965513,342,599 9/ 1967 Reeves 9695 OTHER REFERENCES Prasad et al.: ChemicalAbstracts, vol. 55, pages 2654- J. TRAVIS, BROWN, Primary Examiner US.Cl. X.R.

